Alpha,alpha,alpha&#39;,alpha&#39;-tetrakis(4-hydroxy-3,5-disubstituted phenyl)xylene

ABSTRACT

A NEW SERIES OF COMPOUNDS DEFINED BROADLY AS A,A,A&#39;&#39;,A&#39;&#39; - TETRAKIS(4 - HYDROXY-3,5-DISUBSTITUTED PHENYL) XYLENES WHICH ARE USEFUL AS ANTIOXIDANTS FOR ORGANIC MATERIALS NORMALLY SUBJECT TO OXIDATIVE DETERIORATION, IS DISCLOSED.

United States Patent 3,836,590 ALPHA,ALPHA,ALPHA,ALPHA'-TETRAKIS(4 HY- DROXY-3,5-DISUBSTITUTED PHENYL)XYLENE Gordon D. Brindell, Crystal Lake, and Joseph P. Wuskell, Barrington, Ill., assignors to The Quaker Oats Company, Chicago, Ill. No Drawing. Filed May 12, 1972, Ser. No. 252,859 Int. Cl. C07-c 39/16 US. Cl. 260-619 A 10 Claims ABSTRACT OF THE DISCLOSURE A new series of compounds defined broadly as a,a,a,a tetrakis(4 hydroxy-3,S-disubstituted phenyl) xylenes, which are useful as antioxidants for organic materials normally subject to oxidative deterioration, is disclosed.

BACKGROUND OF THE INVENTION Field of the Invention This invention relates to a new class of antioxidants.

Description of the Prior Art Tetra-2,5-disubstituted phenolic derivatives of phthalaldehyde having the following formula are known as antioxidants:

- x l.. ..l i @J. L@

wherein R is 0-, m-, or p-phenylene and X and Y are alkyl groups.

" We have unexpectedly found that the tetra-2,6-disubstituted phenolic derivatives are superior antioxidants.

SUMMARY OF THE INVENTION Accordingly, one object of the present invention is to provide a novel tetraphenolic derivative of phthalaldehyde which is useful as an antioxidant.

Another object is to provide an organic material normally tending to undergo oxidative deterioration which has been stabilized with a novel tetraphenolic derivative of phthalaldehyde.

Other objects will be apparent to one skilled in the art in view of the following description of the invent Q vvThe objects of this invention are accomplished by a composition having the formula:

wherein R R R and R are independently selected from the group consisting of alkyl and aralkyl and R is 0-, m-, or p-phenylene.

f The objects of this invention are further accomplished by organic material normally tending to undergo oxidative deterioration in the presence of air or oxygen containing an eifective amount of a composition having the above formula.

By alkyl in the formula we mean methyl, ethyl, propyl, butyl penty'l, hexyl, heptyl, etc. and where the alkyl group contains three or more carbon atoms may be straight or branched chain. We prefer that the alkyl group contains from one to ten carbon atoms. Preferred alkyl group include for example, methyl, ethyl, isopropyl, is'o'butyl, sec-butyl, tert-butyl, l-methylbutyl, tert-pentyl,

ice

Z-methylbutyl, neopentyl, l-methylpentyl, 1,1-dimethylpentyl, l-ethylpentyl, 1,1-diethylpentyl, 2-methylpentyl, 2,2-dimethylpentyl, Z-ethylpentyl, 2,2-diethylpentyl, 1- methylhexyl, 1,1-dimethylhexyl, l-ethylhexyl, Z-methylhexyl, 2,2-dimethylhexyl, Z-ethylhexyl, etc.

The aralkyl in the formula may be benzyl, styryl chlorobenzyl, bromobenzyl, iodobenzyl, fluorobenzyl, methoxybenzyl, ethoxybenzyl, methylbenzyl, ethylbenzyl, or tert-butylbenzyl for example. We prefer that the aralkyl group contains less than 20 carbon atoms. Where the alkylene portion of the aralkyl group contains two or more carbons, the alkylene group may be straight or branched chain. We prefer that the aralkyl group is substituted with a group which is halo, alkoxy, or alkyl. Any substitution is on the aryl portion of the aralkyl group and may be made for one or all of the available hydrogens. Suitable halo groups include chloro, bromo, iodo, and fluoro. Suitable alkoxy and alkyl groups include those containing from 1 to 13 carbon atoms.

Exemplary tetra-2,6-disubstituted phenolic derivatives of phthalaldehyde include the following:

a,a,u,a-tetrakis 4-hydroxy-3,S-dimethylphenyl) Xylene; a,a,a',a'-tetrakis (4-hydroxy-3 ,S-diethylphenyDxylene; a,a,oz',oc'-tetrakis (4-hydroxy-3,5-dipropylphenyl)xylene; a,a,a',a'-tetrakis (4-hydroxy-3,5-dibutylphenyl) xylene; a, x,a,a-tetrakis (4-hydroxy-3,S-dipentylphenyl)xylene; a,a, m',a-tetrakis 4-hydroxy-3 S-dihexylphenyl) xylene; ot,m,ot',ol.'-l8tlflkl5 (4-hydroxy-3,5-

diisopropylphenyl xylene; 11,11,u',a'-tetrakis(4-hydroxy-3,5-di-secbutylphenyl xylene; a,a,a',a-tetrakis (4-hydroxy-'3,5-di-tertbutylphenyl) xylene;

methylbutyl phenyl ]xylene; a,a,a,a'-tetrakis(4-hydroxy-3,5-di-tertpentylphenyl) xylene; a,a,rx',a'-te trakis [4-hydroxy-3,5-

di (Z-methylbutyl phenyl] xylene; a,o ,a'-tetrakis(4-hydroxy-3-,5- dineopentylphenyl xylene; a,oz,ct',a'-ieirakiS [4-hydroxy-3 ,5-

di l-methylpentyl phenyl xylene; a,a,a',a'-tetrakis[4-hydroxy-3,5-di(1,1-

dimethylpentyl phenyl xylene; a,a,a',a'-tetrakis [4-hydroxy-3 ,5-di(1- ethylpentyl phenyl xylene; a,a,a,a'-tetrakis[4-hydroxy-3,5-di( 1,1-

diethylpentyl phenyl] xylene; a,u,a',a'-tetrakis [4-hydroxy-3 ,5-di(2- methylpentyl phenyl] xylene; a,u,a',a'-tetrakis [4-hydroxy-3,5di (2,2-

dimethylpentyl phenyl xylene; a,a,a',a'-tetrakis [4-hydroxy-3,5di( 2- ethylpentyl) phenyl] xylene; a,a,a',u'-tetrakis [4-hydroxy-3,5-di(2,2-

diethylpentyl) phenyl] xylene; a,u,oz',ot'-ieirakis [4-hydroxy-3,5-di( 1- methylhexyl phenyl] xylene; a,a,u,a-tetrakis [4-hydroxy-3,5-di( 1- methylhexyl phenyl] xylene; a,u,a',a-tetrakis[4-hydroxy-3,5-di( 1,1-

diethylhexyl) phenyl] xylene; a,a,a',a-tetrakis[4-hydroxy-3,5-di (2- methylhexyl) phenyl] xylene; a,a,m',a'-tetrakis [4-hydroxy-3 ,5-di (2,2,-

dimethylhexyl phenyl] xylene; a,a,a',a'-tetrakis[4-hydroxy-3,5-di (2- ethylhexyl phenyl] xylene; oz,u,cc',oz'-tetlakis [4-hydroxy-3,5-di(2,2-

diethylhexyl phenyl] xylene;

a,a,a',a'-tetrakis(4-hydroxy-3,S-dibenzylphenyl) xylene; u,u,a',a-tetrakis [4-hydroxy-3 ,5-

di p-chlorob enzylphenyl] xylene; a,a,a',u'-tetrakis [4-hydroxy-3,5-

di(p-bromobenzyl phenyl xylene; a,a,a',a'-Btl'akis [4-hydroxy-3,5-di(piodobenzyl phenyl] xylene; a,tx,u',a'-tetrakis [4-hydroxy-3,5-di pfluorobenzyl phenyl] xylene; a,a,a',u'-tetrakis [4-hydroxy-3,5-

di nonylbenzyl phenyl] xylene; a,a,u,et-tetrakis [4-hydroxy-3,5-di (pmethoxybenzyl phenyl] xylene; a,a,a',a-tetrakis (4-hydroxy-3-tert-butyl-5- methylphenyl) xylene; a,m,a',a-tetrakis (4-hydroxy-3,S-distyrylphenyl xylene; a,a,a',a'-tetrakis [4-hydroxy-3,5-di'(pmethylbenzyl)phenyl]xylene; and a,a,a',a-tetrakis [4-hydroxy-3 ,5-di(ochlorobenzyl phenyl] xylene.

The tetraphenolic derivatives of our invention may be obtained by permitting substantially four moles of a phenol to react with phthalaldehyde in the presence of an acidic catalyst.

The reaction is preferably carried out in an inert solvent, for example an alcohol such as methanol, ethanol, 2-propanol, ethylene glycol, ethylene glycol monoethyl ether, etc. Ethanol is the preferred solvent since it allows solubility of the reactants and, in many cases, crystallization of the product directly from solution. The reaction is most conveniently carried out at the refiux temperature of the solvent for 0.5 to about 24 hours. We prefer the reaction temperature to be about 60 C. to 65 C. In those cases where the product does not precipitate on cooling, it may be readily isolated by removal of the solvent or by dilution with water. Liquid products may be isolated in this manner.

Suitable phenols for use in preparing the tetraphenolic compounds include those of the formula:

wherein R and R are consistent with R R R and R as defined above. All of the suitable phenols are commercially available or readily prepared by known tech niques.

The reaction is preferably carried out in the presence of an acid catalyst. Acidic catalysts include organic acids, inorganic acids, and Friedel-Crafts catalysts. Suitable organic acids for example are the phosphoric and sulfonic acids such as phosphoric acid, pyrophosphoric acid, ethanesulfonic, benzenesulfonic acid, toluenesulfonic acid, and naphthalenesulfonic acid. Suitable inorganic acids include the mineral acids such as sulfuric acid and hydrochloric acid. Friedel-Crafts catalysts including aluminum chloride, boron trifluoride, ferric chloride, zinc chloride, and the like, may also be employed.

The catalysts are employed in a catalytic amount which depends on the reactants and reaction conditions. For example, the amount may ranuge from about 2 to 500 parts of catalyst per 100 parts by Weight of the phenol. Preferred concentrations of the catalyst are about 80 to about 150 parts on the same basis.

The tetraphenolic compounds of our invention are useful as antioxidants for organic materials normally tending to undergo oxidative deterioration. By organic material normally tending to undergo oxidative deterioration, we mean to include material based in whole or in part on a skeleton comprising interconnected carbon atoms which upon exposure to oxygen or air loses its desirable properties and becomes weak, brittle, cracked, discolored, viscous or the like. Exemplary organic materials are polymers; hydrocarbon liquids, particularly gasoline and lubricating or fuel oils, hydrocarbon solids or semi-solids, such as waxes, greases and the like; elastomers, such as natural and synthetic rubber; and feeds or foodstuffs.

Typical polymers include polyolefins, polyurethanes, polyethers, and polyamides. Suitable polyolefins include for example polystyrene, polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinyl butylral, polymethyl acrylate, ethylene vinyl acetate copolymers, and ethylene propylene terpolymers. Suitable polyethers include for example polyformaldehyde and polytetramethylene ether glycol.

Hydrocarbon liquids stabilized by our novel tetraphenolic derivatives include motor lubricating oils, gear and transmission fluids based on hydrocarbon oils, and the like. Fuel oils, such as furnace oils and light kerosene fractions, including gas turbine fuels, are also stabilized by our compositions.

Solid or semi-solid hydrocarbons, such as wax and grease, are also improved by incorporation therein of the tetraphenolic compounds of this invention.

Such solid polymeric elastomers as natural and synthetic rubber are stabilized against hardening, cracking, and checking with the tetraphenolic derivatives described. Exemplary of natural rubbers is Hevea brasiliensis, while synthetic rubbers include styrene-butadiene rubber; polybutadiene; polyisoprene; neoprene; butyl rubber; nitrilebutadiene rubbers, styrene-chloroprene rubbers; acrylatebutadiene rubbers; and polyurethane rubber.

The tetraphenolic derivatives of this invention are also useful to enhance the stability of the natural fats and stabilized with our compositions: shortening, lard, butter, coconut oil, cotton seed oil, soybean oil, palm oil, corn oil, peanut oil, sunflower seed oil, safiiower oil, olive oil, and the like or mixtures thereof. These oils may have been treated, as by hydrogenation, interesterification, or fractional crystallization, to modify their melting points.

In general the tetraphenolic derivatives of our invention should be used with the organic material to be stabilized in an amount effective and sufificient to stabilize the material. The requisite amount will, of course, depend both on the efficiency of the particular tetraphenolic derivative and on the nature of the normally oxidizable substrate in which it is employed. It has been our experience that from 0.01 percent to 10 percent by weight based on the Weight of the organic material is sufficient. Amounts down to as little as 0.0001 percent by weight may be effective in some cases.

It is to be understood that the stabilizing effect of the tetraphenolic compounds is considerably enhanced by conventional synergists such as certain sulfides and polysulfides. The synergist is used in conventional amounts. For example, an amount of synergist from about 0.1 percent to about 1 percent by weight of the organic material to be stabilized is satisfactory but we prefer to use from 0.1 percent to 0.5 percent by weight.

As sulfides there may be mentioned dialkylsulfides, particularly wherein the alkyl groups are long chain such as dodecyl groups since the lower dialkylsulfides are too volatile to be effective, di(substituted)alkylsulfides particularly esters of bis-carboxyalkyl sulfides such as dilauryl, distearyl, ditridecyl, or dioctadecyl thiodipropionates or thiodibutyrates, dibenzylsulfide such as bis(Z-hydroxy-S methylbenzyl) sulfide and bis( 3-tert-butyl-Z-hydroxy-S-methoxybenzyl)sulfidc, diaryl sulfide, sulfides such as diphenyl sulfide, dicresyl sulfide, 2:2-dihydroxy-5:S'-dimethyl diphenyl, diphenyldisulfide, dialkyldithiophosphates such as bis(diisopropyldithiophosphoryl)disulfide, and dialkyldithiophosphatomethylphenols.

It will further be understood that the organic material in addition to containing a stabilizing amount of tetraphenolic compound and a synergist may contain such other ingredients as other antioxidants, coloring agents, fillers, curing agents, etc.

DESCRIPTION OF THE PREFERRED 6 Example 4 A number of candidate antioxidants were evaluated in cis-polyisoprene. The results of these tests are set forth in Table III. Cis-polyiosprene was cut up into small pieces H 5 and dissolved overnight in a rapidly stirred solution of EMBODIMENTS 500 ml. of toluene. If the antioxidant was readily soluble The following embodiments of this invention are m toluene 0100 was i added. 9 t prene-toluene solution and stlrred untll 1t dissolved. If the shown for the purpose of illustrating the 1nvent1on and antioxidant was not readily soluble 1n toluene it was d1sdemonstrating the best mode for practiclng the mven- 10 solved in a small amount of an a m riate solvent and tion. It will be apparent to those skilled in the art that PP P various changes and modifications may be made therein without departing from the spirit and scope of the invention as it is more precisely defined in the subjoined claimsi. TABLE HI Example 1 Maximum I V Test protection No. (hours) In a 500 ml. 3-neck flask equlpped w1th a st1rrer, con- X k 11 B 0.5 denser, mtrogen mlet, and a thermometer, 50 ml. of 12mm ajgzahtemkis(H1ydmxy 3,5mmethylphenyn 8 methanol and ml. of concentrated sulfuric ac1d were 20 13 p-xyle r11e.t 4h dr qr h 1 h admixed and cooled to 15 C. Then 6.7 g. of terephthal- 13 35; m y yp enyl)" 3 aldehyde, 42 g. of 2,6-di-ter t-butyl phenol, and 50 m1. of 14 a Y Y-B u Y 13 met ylphenyDp-xylene. methanol were comblned m a beaker and immedlately 15 t 'itggfakii(4-hsidroxy-3-tert-butyl-fi- 6 me 611 X ene. added to the stlrred m1xture 1n the fiask. The reacuon 5 16 ,jg g g g 7 mlxture was then held at 65 C. under a mtrogen atmos- 17 propyllznhtena3lg )pixgleire. 3 5m 7 phere for 5 hours. The reaction mixture was then cooled g;,";f 1,,f ,,;i ,g,, to room temperature (27 C.) and allowed to stand over- 18 a iS( -hydr0Xy-3,fi-diisobutylo phenyDp-xyiene. mght. The product was separated from the reacnon m1X- 19 a,a,a,atetrakis(4-hydl0Xy-3,5-d1-i6Tt- 16 ture'by filtration, was triturated with ethanol, washed 20 gij fyggg ggfligi- 3 with water until the water washes were neutral, and dried e v ylp e v )l y i o I 21 a,a,a,a'-tetrak1s(4-hydroxy-3,5-dibenzylphenyl)- 7 in an oven at 50 C. grxylene.

The product was identified as a,a,u',a'-tetrakis(4-hy- 22 18. i hydr0Xy-3,5di-4-methy1- e enzylphenyl) p-xylene. droxy 3,5-d1-tert-buty1pheny1)p-xylene. Analys1s of the product laiforded the following data: M.P. between 272 C. and 281 C., and analyzing to C, 83.1 percent; H, 10.0 percent. (2 11 0 requires C, 83.2 percent; H, 9.8 Percent then added to the toluene solution. A sample of the solu- J 2 40 tion was then taken up in a capillary dropper and 15 drops were placed on a circular sodium chloride plate, Usleg the l the fonewmg tetra 1 inch in diameter. The plate was then put in a 130 C. h m tdenvatlves. were' Wadlly Prepared excellent oven for a few minutes to evaporate the toluene. W Q-i WP noted, were found to have An infrared spectrum was run of the film on the plate. the, properties reported. 1n Tabled. The plate was then put back in the oven. Every hour it TABLE I Composition (percent by weight) Calculated Found Test M. No. Phenol Rmduet tetraphenolic derivative C.) C H C H 1 2,6-dimethylphenol; a,q,a-tetrakis(4-hydroxy-3,5- 254-259 31,9 7,2 $1.23 7.4

flimethylphenyl) p-xylene. 2 2,6-diisobuty1phenol... ,a, ',a'-tetrakis(4-hydroxy-3,5- 149-151 83.2 9.8 83.5 9.9

. I diisobutylphenyl) p-xylene.

Example 3 was removed and another infrared spectrum was run. Again usingwthe method of Example I, the following ghs PfiOCBduI'fi was repeated unt1l appreciable oxidatlon tetraphenolic derivatives were prepared in excellent place as mdlcated the appearance of a yields from the phenolsnoted and were found to have the Ony and at 1700 175 0 The test waeended e 1 d o the carbonyl band exceeded 6 cm. on a Perkm Elmer Inme ting po1nts reporte 1n Ta e v TABLE, H v frared Spectrophotometer, Model 710. Th 1s length'ls ap- I v I proximately equal to the length of' the peak at 1450 cmr Test M.P. No. Phenol Product tetraphenolic derivative 0.) Example 5 3 2-tert-glutlylilfi- 1 egg,iz'f-fietlzgiif(ghydfioxy-ii-iert- 219-221 me yp eno. uy--me yp en p-x ene. 4 zwiisopmpyb aqa,Mtetmkis(4 hdmxi3,5 17H" A5 nurlnblelr 12f candidate stabilizers were mcorporated 2 gggc buty1 dflseprgggrfglfiggabggzggyznes 159 162 1n 1 m t 1c samples of polypropylene film, and the 5- mem phenol, di 8ec buty1phenyl pxylege. resu ting materlals evaluated by heat aging the films. In 2 (;1-di-2l-etl',1hy1-l 1,3 65,fittifi kgufi qf f. 1 some of the tests where mdlcated dllaurylthiodipropionate ex eno 1 -e y exy en x ene. 7 2,6-di e r 1zyl- 01,11,111, a tetrakisgi-n dn as- 179-184 was added as eyneljglst' phgnoL dibepzylphenylmxylem In the heat aglng test, polypropylene film samples 5 8 fig 183-183 ml 1n thlckness were maintained in an oven at 140 C.

enzylphenol. dl-methylbenzylphenyi)1r-xy1ene. gag l h ,5 ki lflgeigakifigrj-hy?roxy-3 fi. 324-330 Each sample was tested for loss of structural 1ntegr1ty.

8110 tme en 11 ene.

10 l; ,l g g y sown The number of hours shown 1n the table are the total methylphenol. tert-butyl-G-methylphenyl)pelapsed hours before the film cracked or embnttled when xylene flexed. The film was embrittled when it crumbled to a 1 011 at 27 C.

powder.

The resulting data are presented in Table IV. bility than the 2,5-derivatives in typical alcohol and hy- TABLE IV Percent by weight Tetra- Oven hours Te phenolic Syner- No Compound derivative gist Cracked Embrlttled 23-..... Blank 0 1 27 24..." a,a ,d,a-tetrakis(4-hydroxy-3,5 0.1 0 31 31 dimethylphenyl) p-xylene. 25--." a,oz,o/,a-tetrakis(4-hydroxy-3,5-dimethyl 0. 1 0. 3 602 644 phenyDp-xylene plus dllaurylthiodlpropionate. 26. a,a,a,a-tetrakls(4-hydr0xy-3,6 0. 1 0 30 30 dimethylphenyl) p-xylene. 27...- 0,0: a,a'-tetrakis(4-hydroxy-3,6-dimethyl 0. 1 0. 3 500 507 phenyl) p-xylene plus dilaurylthiodlpropionate.

Example 6 The solubility of some of the tetraphenolic derivatives prepared above in ethanol and toluene at 27 C. is reported in Table V.

butyl-G-methylphenyl) p-xylene.

The above Examples clearly demonstrate the accomplishment of this invention. Example 1 demonstrates our best mode for preparing the novel tetraphenolic derivatives of our invention.

Examples 2 and 3 further demonstrate the best mode of practicing our invention. Tests 1-8 inclusive are embodiments of our invention. Tests 9-10 inclusive are not embodiments of our invention but were prepared for the purpose of comparison with our compositions in these and in the following examples. A comparison of the melting point given in Test 1 with Test 9 and a comparison of that in Test 3 with Test 10 shows that the tetra-2,6-disubstituted phenolic derivatives of our invention have lower melting points than the 2,5-derivatives.

In Example 4 a comparison of Tests 12 and 14 with Tests 13 and 15 respectively clearly demonstrates that our tetra-2,6-disubstituted phenolic derivatives are unexpectedly superior to the 2,5-derivatives as antioxidants in cis-polyisoprene. Tests 1 6-22 inclusive further indicate the efiectiveness of our compositions as antioxidants in cispolyisoprene.

In Example 5, a comparison of Test 24 with Test 26 and more particularly of Test 25 with Test 27 shows the unexpected superiority of our tetra-2,6-disubstituted phenolic derivatives over the prior art 2,5-derivatives. The superiority of our compositions as stabilizers for polypropylene is most evident when used in conjunction with a synergist.

Example 6 demonstrates by comparing Test 28 with Test 29 and Test 30 with 31 that our tetra-2,6-disubstituted phenolic derivatives have the same or greater soludrocarbon solvents. This facilitates easier distribution in organic material to be stabilized.

From the foregoing descriptions we consider it to be clear that the present invention contributes a substantial benefit to the antioxidant art by providing a new and useful antioxidant suitable for stabilizing organic materials normally tending to undergo oxidative deterioration.

We claim:

1. A composition having the formula:

wherein R R R and R are alkyl, and R is p-phenylene.

2. The composition of Claim 1 wherein the alkyl group contains from 1 to 10 carbon atoms.

3. The composition of Claim 1 wherein the alkyl group is selected from the group consisting of methyl, ethyl, isopropyl, sec-butyl, isobutyl, tert-butyl, and 2-ethylhexyl.

4. The composition of Claim 1 which is a,a,a,a'-tetrakis(4-hydroxy-3,S-dimethylphenyl)p-xylene.

5. The composition of Claim 1 which is a,a,a,a'-tetrakis (4-hydroxy-3 ,S-diisopropylphenyl p-xylene.

6. The composition of Claim 1 which is a,a,a',o='-tetrakis 4-hydroxy-3,S-diisobutylphenyl) p-xylene.

7. The composition of Claim 1 which is u,a,a',a'-tetrakis (4-hydroxy-3,S-di-sec-butylphenyl p-xylene.

8. The composition of Claim 1 which is a,a,a',a'-tetrakis (4-hydroxy-3 ,5 -ditert-butylphenyl p-xylene.

9. The composition of Claim 1 which is u,u,a',a-tetrakis [4-hydroxy-3,5-di 2-ethylhexyl] p-xylene.

10. a,a,a',a'-Tetrakis(3 methyl-4-hydroxy-S-Iert-butylphenyl-) p-xylene.

References Cited UNITED STATES PATENTS 6/1963 Schwartzer 260-619 A X 3/1967 Hurlock et al. 260-619 A X US. Cl. X.R.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,836,590 .Dated eptember 17, 197 4 lnvgentoflsl) Gordon D. Brindell and Joseph P; Wuekell It is certified that error appears in the ebove-identified patent anclwthat said Letters Patent are hereby corrected as shown below:

Coinm ri l, line 35 after "and" insert --oils. For example the following edible oils can be--.

Signed and sealed this 24th day of December 197 .v

- (SEAL) -Atte stz McCoy M. GIBSON JR. c. MARSHALL DANN- Attesting Officer Commissioner of Patents FOFi'QM So-"959N036, '7 v USCOMM-DC scan-eon I U.$. GOVERNMENT PRiNI'ING OFFICE I"! 0-85-384.

I UNITED STATES PATENT- OFFICE CERTIFICATE OF CORRECTION Patent No. 3, 3 ,59 v 1 I Da d September 17, 197 l Gordon D. Brindell and Joseph P. Wuskell It is certified that error appears in the above-identified patent am} that said Letters Patent are hereby corrected as shown below:

Column 4, line 35 after "and" insert --o:'Lls. For example the following edible oils can be--.

Signed and sealed this 24th day of December 1974. I

(SEAL) Arrest:

McCC-l M. cxasom JR. c. MARSHALL DANN Attesting Officer Commissioner of Patents FORM 9 7 uscoMM-oc-aoan-Peo r u.s. eovumu'nr manna ornc: ma q-su-su. 

